Phenyl sulfonyl triesters of nitro alcohols



Patented Dec. 3, 1946 PHENYL SULFONYL TRIESTERS OF NITRO ALCOHOLS PhilipJ. Baker, Jr., Terre Haute, Ind., assignor to Commercial SolventsCorporation, Terre Haute, Ind., a corporation of Maryland No Drawing.Application July 9, 1945, Serial No. 604,083

1 4 Claims.

The present invention relates to new chemical compounds and is acontinuation-in-part of my copending application Serial No. 521,125,filed February 4, 1944.

More particularly my invention relates to phenyl sulfonyl esters ofnitro alcohols. The new chemical compounds of my invention may berepresented by the following general structural formula:

wherein X represents a substituent of the group consisting of hydrogen,alkyl and acylamino, and Ar represents a phenyl nucleus.

As examples of compounds included by the abov generic formula there maybe mentioned tris (p toluenesulfonoxymethyl) nitromethane, tris(benzenesulfonoxymethyl) nitromethane, tris (pacetamidobenzenesulfonoxymethyl) nitromethane, and the like.

In accordance with my invention, compounds of the above type areprepared by first mixing a trihydric nitro alcohol with a phenylsulfonyl halide and thereafter slowly adding to this mixture a suitablebase, such as, for example, a tertiary amine. The nitro alcohol andphenyl sulfonyl halide are preferably reacted with one another inapproximately equivalent quantities while the tertiary amine isgenerally preferably employed in a quantity slightly in excess of theequivalent amount. The initial reaction is rather vigorous andprecautions should therefore be taken in order to avoid decomposition ofthe reactants. After the initial stage of the reaction has beencompleted, however, the reaction mix ture is preferably heated to atemperature of between about 80 and 100 C. so that the reaction isdriven as nearly to completion as possible. The resultant mixture isthen cooled, and water is added in order to remove the hydrogen halideof the tertiary amine and any unreacted alcohol which may be present. Atthis stage of the procedure, the ester will generally be observed tosolidify. The product is then filtered and washed with water. In mostcases the esters can be crystallized either from methanol or ethanol.Frequently benzene or similar hydrocarbons can be used for this purpose.

The nitro alcohol utilized in preparing the new phenyl sulfonyl estersof my invention is tris (hydroxymethyl) nitromethane.

As examples of tertiary amines which may be utilized in synthesizing thecompounds of my invention, there may be mentioned pyridine,trimethylamine, tributylamine, quinoline, and the like. Bases such assodium carbonate and sodium hydroxide may also be employed in place oftertiary amines; however, it has been my general observation that theresults obtained when using such bases are less satisfactory. Solvents,such 2 as benzene, chloroform, and xylene, may be employed. However, ithas usually been found that the yield of the desired aryl sulfonyl esteris lower when a solvent is utilized.

My invention may be further illustrated by the examples which follow.

Example I A mixture of 3.8 parts of tris (hydroxymethyl) nitromethaneand 13.4 parts of p-toluenesulfonyl chloride was placed in a reactionvessel and 6 parts of pyridine were slowly added thereto. The reactionmixture was cooled for a short period and then warmed gently over steamfor 15 minutes. To the reaction mixture water was added and the mixturecooled and filtered. The solid product, namelytris(p-toluenesulfonoxymethyl)nitromethane, was filtered andrecrystallized from methanol yielding 3.6 parts of product correspondingto a 23.5% yield. Its melting point was 122 to 123 C.

Analysis. Calculated for: N, 2.28; S, 15.66. Found: N, 2.32; S, 15.40.

Example II Using the procedure described in Example I, and reactingtris(hydroxymethyl)nitromethane with benzenesulfonyl chloride, theproduct tris (benzen'esulfonoxymethyl) nitromethane was prepared andfound to have a melting point of 122 to 123 C., a nitrogen content of2.88% as compared to a theoretical nitrogen of 2.45% and sulfur contentof 17.9% as compared to a theoretical sulfur value of 16.8%.

Although the physical properties given for the two compounds may behelpful in identifying them, it is to be understood that I do not limitmyself to products having the exact physical constants described, sincethe data were obtained from single preparations of the compounds listed.

The phenyl sulfonyl esters of my invention are useful for numerouspurposes, particularly as plasticizers for synthetic rubber and similartype polymers. Other uses of these products will readily occur to thoseskilled in the art.

My invention now having been described, what I claim is:

1. Phenyl sulfonyl esters of nitro alcohols having the formula No.X-Al'-SO2-OH2C( JCH20-SO2AIX CHiOSOg-ArX wherein X represents asubstituent of the group consisting of hydrogen, alkyl and acylamino,and Ar represents a phenyl nucleus.

2. Tris(p toluenesulfonoxymethyl) nitromethane.

3. Tris (benzenesulfonoxymethyl) nitromethane.

4. Tris(p-acetamidobenzenesulfonoxymethyl nitromethane. 1

PHILIP J. BAKER, JR.

